US3009017A - Laminated television screen - Google Patents

Laminated television screen Download PDF

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US3009017A
US3009017A US356684A US35668453A US3009017A US 3009017 A US3009017 A US 3009017A US 356684 A US356684 A US 356684A US 35668453 A US35668453 A US 35668453A US 3009017 A US3009017 A US 3009017A
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plastic
sheet
glass
laminated
television
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US356684A
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Harry E Conner
Paul T Mattimoe
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Libbey Owens Ford Glass Co
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Libbey Owens Ford Glass Co
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86Vessels; Containers; Vacuum locks
    • H01J29/863Vessels or containers characterised by the material thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18Luminescent screens
    • H01J29/24Supports for luminescent material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/86Vessels; Containers; Vacuum locks
    • H01J29/87Arrangements for preventing or limiting effects of implosion of vessels or containers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2229/00Details of cathode ray tubes or electron beam tubes
    • H01J2229/87Means for avoiding vessel implosion
    • H01J2229/875Means substantially covering the output face, e.g. resin layers, protective panels

Definitions

  • the present invention relates broadly to laminated glass structures, and is more particularly concerned with a laminated glass light filter suitable for use as an implosion plate in television receivers.
  • Another object of the invention is to provide a television screen which is characterized by its substantial free.- dom from objectionable light scattering effects, and which is possessed of no coloration which deleteriously alters the picture and reflection coloration.
  • Another object of the invention lies in the provision of a television screen having improved attenuation in the maximum light output regions of the television tube and improved attenuation in other spectral regions.
  • a further object of the invention is to provide a light filter for television screens which substantially reduces glare and eye strain, and which comprises one or more glass sheets and a plastic interlayer treated with a suitable dyestutf to impart to said filter the foregoing noted improved characteristics.
  • a further object of the invention is to provide a laminated television screen having a plastic interlayer securing a pair of glass sheets in unitary relation, which interlayer preferably has an index of refraction substantially the same as that of the glass and which is dyed with a substance which imparts fast and clear color to the interlayer.
  • a still further object of the invention lies in the provision of a method of producing laminated television screens comprising dyeing a plastic interlayer with a suitable dyestuff, assembling the interlayer between sheets of glass, and applying heat and pressure to the assembly to bond the same into a composite structure.
  • FIG. 1 is a perspective view of a laminated television screen of this invention
  • FIG. 2 is a diagrammatic perspective view of apparatus suitable for dyeing plastic sheeting employed as the interlayer in the present screen;
  • FIG. 3 is a curve showing the light output of the phosphor which is used in many commercial television picture tubes
  • FIGS. 4, 5 and 6 are spectral transmittance curves of typical television screens embodying the features of the invention herein disclosed.
  • FIG. 7 is a diagrammatic view showing the television screen positioned in front of a cathode ray tube.
  • a light filter or viewing screen for television receivers comprising one or more sheets of a transparent material such as glass, either clear or tinted, and a plastic layer bonded thereto, said layer being preferably formed of a thermoplastic resinous material such as polyvinyl butyral which has been treated with a solution which may com- Patented Nov. 14, 1961 prise an alcohol, water, and a molecularly dispersed organic dyestuff such as Capracyl Black N with or without additives, which may be Capracyl Blue G or Anthraquinone Blue SWF.
  • a thermoplastic resinous material such as polyvinyl butyral which has been treated with a solution which may com- Patented Nov. 14, 1961 prise an alcohol, water, and a molecularly dispersed organic dyestuff such as Capracyl Black N with or without additives, which may be Capracyl Blue G or Anthraquinone Blue SWF.
  • light filters may be produced which have a total visible luminous transmittance (LCJ. Ill. A) ranging between 30 and and a haze factor of not more than one percent.
  • LCJ. Ill. A total visible luminous transmittance
  • the noted dyestuffs are molecularly dispersed, it is of course possible, depending upon the concentration of solution, temperature, and type of solvents, that they be associated to a greater or lesser degree.
  • Capracyl Black N and Blue G dyestuffs which have been found particularly suitable to accomplish the purposes of the present invention are neutral dyeingrnetallized azo dyes.
  • Capracyl Black N is listed in the Technical Manual of the American Association of Textile Chemists and Colorists, vol. XXXV, part 5, 1959 edition on page 244, right-hand column line 32; and the color index number of Capracyl Blue G is Acid Blue 165.”
  • Anthraquinone Blue SWF is identified as prototypeNuInber 12. (Color Index No. Acid Blue 25).
  • FIGURE 1 a laminated television screen or light filter, designated in its entirety by the numeral 10,'which comprises a pair of glass sheets 11 and 12 anda plastic interlayer 13 bonded under heat and pressure to the inner face of each of said glass sheets.
  • the glass forming said sheets is preferably that often referred to as ordinary clear sheet glass, although in cetrain instances it may be found desirable to employ a tinted glass characterized by a somewhat different chemical composition.
  • Ordinary sheet glass, preferably of double strength weight, and having no perceptible color is, however, effective to accomplish the purposes of this invention.
  • Glass of'this type has a general composition approximating 72.80% SiO 0.15% Fe O 0.90% A1 0 0.50% TiO 8.50% CaO, 3.60% MgO, 13.10% Na o, 0.08% K 0, 0.30% 80,, and 0.07% As O
  • the plastic interlayer 13 of the light filter 10 is preferably forrned of polyvinyl butyral resin, and as examples of materials which have been found particularly suitable are those designated as Saflex, manufactured and 'sold by Monsanto Chemical Co., Butacite by E. I. du Pont de Nemours and Co., and fVinal by Carbide and Chemicals Corp.
  • the interlayer 13 preferably comprises parts by weight of polyvinyl butyral resin and either 41 parts by weight of tri-ethylene glycol di-hexoate 0:40
  • dibutoxyethyl adipate parts by weight of dibutoxyethyl adipate. With the latter compound in the amount indicated the resin contains 29% of plasticizer, and with the former, 28.6% of plasticizer.
  • Resinous materials other than polyvinyl butyral may of course be used, such as for example, polyvinyl formal and acetal.
  • the continuous dyeing machine illustrated therein preferably comprises a primary wash section A, a dyeing section B, and a rinse or secondary wash section C. Positioned adjacent the section A is a pair of drive rolls 14 which draws plastic sheeting 15 from a supply roll 16 into the wash section A between hot water sprays 17 and beneath an idler roll 18.
  • the sheeting 15 is then drawn upwardly between cold water sprays 19 by means of a pair of drive rolls 20, and a large portion of the excess water on said sheeting is removed by a pair of wringer rolls 21 adjacent which are compressed air jets 22 for substantially drying the now thoroughly washed sheeting 15.
  • Idler rolls 23 are provided adjacent the base of the dyeing section B and the sheeting passes beneath said rolls and through the dye solution 24 prior to its movement upwardly and between an additional pair of wringer or squeegee rolls 25 which are partially immersed in said solution.
  • the sheeting 15 continues into the rinse or secondary wash section C wherein there are located cold water sprays 26 directed at opposite surfaces of the dyed sheeting and an idler roll 27 under which the plastic matei'ial passes prior to being drawn upwardly between spaced pairs of wringer rolls 28 and 29 by the drive rolls 30.
  • Two spaced pairs of compressed air jets 31 and 32 are located forwardly of said drive rolls, and positioned between said pairs of jets are electric radiant heaters 33 which operate to reduce the dye solution solvent which has been absorbed into the sheeting.
  • a trough of dusting material 34 such as sodium bicarbonate, is provided in the path of the moving plastic material, and after being dusted, said material is rolled up into a form suitable for cutting into sizes for use as an interlayer in the present invention.
  • the plastic is oven-dried to remove last traces of solvent, is then festooned and cut, and is next rapidly washed to remove the sodium bicarbonate dusting powder.
  • the dyeing procedure is preferably initiated by first turning on the water sprays 17 in the wash section A and feeding the plastic sheeting into the dyeing machine.
  • Dye solution 24 is then pumped into the dye section B to a level sufficienjt to partially immerse the pair of squeegee rolls 25 located at the exit end of the dye bath or section B.
  • a supply of water to the rinse section C and compressed air to the jets 22, 31 and 32 is then furnished, and the radiant heaters 33 and motor means (not shown) operating the drive rolls 14, 20, 29 and 30 turned on.
  • Tension is maintained on the platsic, and wrinkling thereof avoided as it passes through the wash sections A and C, by operating the drive rolls 14 at a speed generally about slower than the squeegee or wringer rolls 21,
  • Plastic sheeting dyed in accordance with the disclosed procedure has, when laminated by conventional techniques under heat and pressure between sheets of either clear or tinted glass, a total visible light transmittance (hereinafter referred to as TVLT) with illuminant A of between 30 and and a haze factor or light scattering characteristic of substantially less than one percent, the TVLT being dependent upon the composition and concentration of the dye solution, and the speed of passage of the sheeting through the dyeing procedure.
  • the total visible luminous transmittance of the television screen herein disclosed is preferably determined by optical bench measurements on the unlaminated dyed plastic since experience has indicated that the transmittance value for the dyed plastic alone seldom varies more than one percent from the TVLT of the laminated screen itself when employing ordinary sheet glass.
  • Illuminant A total transmittance may be calculated from the spectral transmission curve of the dyed plastic determined by a spectrophotometer before or after lamination with glass sheets.
  • the haze value depends largely on the nature and composition of the plastic itself, and is readily determined in accordance with A.S.T.M. Designation: D100349T.
  • Example 1 A sheet of polyvinyl butyral having a plasticizer content of approximately 29% was dip dyed for 6% minutes at 75 F. in a dye bath containing 2.5 grams of Capracyl Black N dyestuff dissolved in one liter of a solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of distilled water. A neutral color was produced in the plastic, and optical measurements indicated the plastic had a total visible light transmittance (TVLT) of 43% and a haze factor of 0.9%. The plastic was then laminated between single sheets of double strength sheet glass.
  • TVLT total visible light transmittance
  • Example 2 A sheet of the same type of plastic was dip dyed for 6 /2 minutes at 75 F. in a blended dye bath of two parts by volume of Capracyl Black N as in Example 1 plus one part by volume of blue composed of 2.5 grams of Capracyl Blue G, dissolved in one liter of the same solvent used in the above example.
  • the plastic had a neutral blue color, and a TVLT of 42% and a haze factor of 0.6%. It was then laminated as above.
  • Example 3 A sheet of the same type of plastic was dip dyed for 6 minutes at 75 F. in a blended dye bath containing 2 parts of black to 3 parts of blue by volume.
  • the black bath contained 2.5 grams of Capracyl Black N dyestuff dissolved in one liter of a solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of water.
  • the blue bath was prepared in the same concentration and solvent system with Capracyl Blue G dyestutf.
  • the plastic had a TVLT of 45% and a haze factor of 0.5%.
  • a laminate was then produced as previously.
  • Example 5 A plastic sheet dyed in the same manner as in the second example was laminated between two sheets of a tinted glass as above.
  • the laminate thus formed had a TVLT of 37% and a haze factor of 0.5%.
  • Example 6 A plastic sheet dyed in the same manner as in the third example was laminated between two sheets of a tinted glass as above. It was found that the laminate had a TVLT of 37% and a haze factor of 0.8%.
  • Example 7 A sheet of polyvinyl butyral resin manufactured and sold by Monsanto Chemical Co., under the name Neutralite, and which has carbon black pigment dispersed within the plastic itself, was laminated between sheets of a tinted glass. It was noted that the laminate had a TVLT of 48.5% and a haze factor of 2.37%.
  • Example 8 The same type plastic as in the last example was laminated between two pieces of clear sheet glass. Optical measurements on the laminate produced a TVLT of 57.6% and a haze factor of 1.5%.
  • Example 9 A sheet of monolithic methyl methacrylate plastic proposed for television screens and having a thickness of 0.0575 inch, as compared to 0.015 inch in the last two examples, was ex'amined and found to have a'TVLT of 44.0% and a haze factor .of 3.7%.
  • Example 10 A sheet of the same type polyvinyl butyral resin as in the first six examples was dip dyed for one minute at 75 F. in a dye bath containing 2.5 grams Capracyl Black N dyestuff dissolved in one liter of solvent .composed of 60 pants by volume of ethyl alcohol and 40.parts 'by volume of distilled water. The dyed plastic was rinsed with water and noted to be of a neutral shade. It was found to have a TVLT of 55% and a hazefactor of 0.3%. The sheeting was then laminated with sheets of tinted glass.
  • Example 12 The same type plastic as above was dyed with the same solution as Example 10, the dyeing time being increased to two minutes in the bath. It was noted that doubling the dip time decreased the TVLT to 50% and the haze factor was 0.25%. A laminate of the same structure as above was made.
  • Example 13 The same procedure as in the last example was followed in the dyeing of polyvinyl butyral resin with the dye solution of Example ll.
  • the increase in dipping time reduced the TVLT to 51% and the dyed plastic had a haze factor of 0.3%.
  • a tinted glass was used in making a laminate.
  • Example 14 Polyvinyl butyral sheeting was dipped for one minute at 75 F. in a Capracyl Black N dye bath of the following composition: Two and one-half grams of dyestuif dissolved in one liter of solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of water. The dyed sheeting was found to have a TVLT of 64.5% and a haze factor of less than 1%.
  • Example 15 A dye solution was prepared containing a mixture of sixty gallons of denatured ethyl alcohol and forty gallons of distilled water, to which was added with stirring plastic per minute therethrough, and the solution is prepared as above, the total visible light transmittance (III. A) of the dyed sheeting will continuously remain at 42.5% plus or minus 3.0%, and that the haze factor will be in the neighborhood of 0.25 and 0.35%.
  • a plastic .interlayer for use in television screens may be produced having substantially any particular light transmittance for any specific television tube by accurate control of the composition and concentration of the dye solution, by careful regulation of the rate of feed or time absorbed in passing the plastic through the dye bath, and by selection of the desired type of glass used inthe'laminate.
  • the plastic when combined with sheets or plates of glass, the plastic may be laminated to any desired thickness with an increase in the safety factor by merely using a plastic inter-layer of greater thickness, as for example, to 0.045 inch, or by increasing the number of layers of 0.015 inch plastic.
  • oil soluble type dyestuffs of the proper spectral characteristics may also be employed.
  • oil soluble type dyestuffs of the proper spectral characteristics may also be employed.
  • the oil soluble type dyestuff is dissolved in a plasticizer or solvent plasticizer mixture and then applied to the surface of the sheeting using silk screens or printing rolls.
  • FIGURE 3 a curve of the light output of the P4 phosphor which is used in many of the commercial television picture tubes. From this it may be seen that the particular phosphor plotted peaks or has its maximum light output at slightly less than 440 millimicrons or 4400 Angstrom units when the relative intensity or energy is between 82 and 83, and at about 550 millimicrons or 550 Angstrom units when the relative intensity is about 78.
  • FIGURE 5 plots the spectral transmittance of a television screen which has been manufactured according to Example 4. It will be noted that this screen has a 37.5% transmittance at about 440 millimicrons and substantially the same transmittance at about 550 millimicrons, the peaks of the same phosphor tube as shown in FIG. 3. As was brought out in this particular example, the screen had a total visible transmittance of 38% and a haze factor of 0.6%. Since the dyed plastic was laminated between two sheets of tinted glass, such as screen possesses a high attenuation in the red regions of the spectrum.
  • FIGURE 6 illustrates a curve of wavelength plotted against percent transmittance for a screen produced in accordance with Example 14 and which has a TVLT of 64.5%. It may be seen that such a screen has a transmittance of 614% at 440 millimicrons and 63.7% at 550 millimicrons. It has been found to have particular utility in connection with television picture tubes which have a light output slightly lower than that of the tube plotted in FIGURE 3.
  • the P4 phosphor screen designated as such by the Radio Manufactin ers Association to indicate its use in monochrome (black and white) television, is considered to be a twocomponent screen comprising a blue-emitting and a yellow emitting phosphor.
  • most unalurninized P4 screens for direct viewing kinescopes presently comprise admixed hex.-ZnS:Ag (blue component) and hex.-ZnS(47) CdS(53):Ag (yellow component).
  • These two sulphide phosphors have closely matched emission characteristics as a function of cathode ray current density, and screens made of the two phosphors give uniform white emission in image half-tones andhigh lights.
  • P4 phosphor screens which have been coded by the Radio Manufacturers Association as P4 phosphor screens and with which the present invention is of particularly important application.
  • the first, which may be referred to as P4(a) is understood to be formed of a mixture of hex.-ZnS: Ag(0.0l5) and hex.-l.3 ZnS-CdS:Ag(0.0l).
  • the second, P4(b), presumably consists of hex.-ZnS:Ag(0.)l5) or a mixture of cub.-ZnS:Ag(0.003-0.0l) and rbhdl.- Zn BeSi O :Mn(l.4).
  • the third, P4(c) is understood to comprise as the representative phosphor monocL-Ca Mg(SiO :Ti(l) plus rbhdl.-Zn BeSi O :Mn(1.4).
  • P4 phosphors not only differ in composition but has slightly different peaks or regions of maximum light output.
  • the P4(a) phosphor with which we are most familiar and the light output curve of which is plotted in FIG. 3 of the accompanying drawings peaks at about 4400 and 5500 Angstrom units
  • the P4(b) and P4(c) phosphors peak at about 4600 and 5400 Angstroms and 4000 and 5400 Angstrom units, respectively.
  • each of the noted P4 phosphors have particular utility in television kinescopes of the monochrome type and emit white light both before and after excitation, with the exception of the P4( b) type which emits greenyellow light after excitation only, the present invention is of application to cathode ray tubes utilizing either of these representative phosphors.
  • laminated television screens of the character herein disclosed will be found to attenuate well and to provide improved picture clarity with cathode ray tubes which have regions of maximum light output between 400 and 480 millimicrons and between 500 and 580 millimicrons.
  • FIGURE 7 A cathode ray tube of the above character for' television receivers is illustrated in FIGURE 7, and upon reference thereto, it will be noted that said tube 35 is provided with a picture face 36 carrying on its inner surface a phosphor coating 37.
  • the viewing screen or light filter 10 herein disclosed is positioned in front of and closely adjacent to the picture face 36.
  • the plastic interlayer 13 provided between the glass sheets 11 and 12 of said screen 10 may be formed of a plurality of plastic sheets, one or more of which may be dyed as above described and one or more of which may be of substantially clear undyed plastic.
  • a cathode ray tube provided with a picture face carrying a phosphor coating, and a viewing screen spaced in front of and closely adjacent to said picture face, said phcsphor coating being a member of the group consisting of a mixture of rbhdl.-Zn BeSi O :Mn(1.4)
  • said viewing screen comprises a sheet of glass and a sheet of dyed plastic material bonded to said glass sheet, said plastic material carrying the azo dye.
  • the dyed sheet of plastic material has regions of minimum visible light transmittance between 400 and 460 millimicrons and between 520 and 560 millimicrons.
  • a cathode ray tube provided with a picture face carrying a phosphor coating having two regions of maximum light output, one between 400 and 480 millimicrons and one between 500 and 580 millimicrons, and a viewing screen spaced in front of and closely adjacent to said picture face, said viewing screen comprising a sheet of glass and a sheet of plastic material colored a neutral gray with a metallized azo dyestudf, said colored plastic sheet having a total visible luminous transmittance (I.C.I. Ill. A) effective to attenuate the White light emitted by said tube within both the maximum light output regions of said phosphor to provide better image contrast and clarity as well as picture definition.
  • I.C.I. Ill. A total visible luminous transmittance
  • said phosphor coating being a member of the group consisting of a mixture of hex.-ZnS:Ag(0.0l) and hex-1.3 ZnS-CdS:Ag(0.0l); hex.-ZnS:Ag(0.015) or a mixture of cub. ZnS:Ag(0.003-0.0l) and rbhdl. ln Besi O zMn (1.4); and monocl. CaMg(SiO :Ti(1) plus rbhdl.
  • a viewing Screen spaced in front of and closely adjacent to said picture face, said viewing screen comprising a sheet of glass and a sheet of plastic material bonded to said sheet of glass, said plastic material being colored a neutral grey with a metallized azo dyestuif, said colored plastic sheet having a total visible luminous transmittance (I.C.I. Ill. A) effective to attenuate the white light emitted by said tube within both the maximum light output regions of said phosphor to provide better image contrast and clarity aswell as picture definition.
  • I.C.I. Ill. A total visible luminous transmittance
  • the dyed sheet of plastic material has regions of minimum visible light transmittance between 400 and 460 millimicrons and between 520 and 560 millimicrons.

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Description

Nov. 14, 1961 Filed May 22, 1953 H. E. CONNER ETAL LAMINATED TELEVISION SCREEN 2 Sheets-Sheet 1 Inventory $04k fame attorneys Nov. 14, 1961 -i=dnsmittdnce- Relative Intensity Percent Filed May 22, 1953 wavelength In Millimicvons fig.
400 4 600 640 700 Wave1en5'th In Millimicrons H. E. CONNER ETAL LAMINATED TELEVISION SCREEN 2 Sheets-Sheet 2 Percent Transmittdnce 400 440 $00 600 640 700 Wavelen5'th In Mi1limicrons Percent Tmnsmittdnce 400 140 $00 540 600 640 Wavelength In Millimicrons fig. 6
f6 1 Jnventom 072m: mad! WJ W attorneys United States Patent O-"ice 3,009,017 LAMINATED TELEVISION SCREEN Harry E. Conner and Paul T. Maltimoe, Toledo, Ohio,
The present invention relates broadly to laminated glass structures, and is more particularly concerned with a laminated glass light filter suitable for use as an implosion plate in television receivers.
It is an important aim of the present invention to providea television screen which grants improved contrast to television images in either a bright or darkened room, and which also imparts to said images substantially increased clurity and definition.
Another object of the invention is to provide a television screen which is characterized by its substantial free.- dom from objectionable light scattering effects, and which is possessed of no coloration which deleteriously alters the picture and reflection coloration.
Another object of the invention lies in the provision of a television screen having improved attenuation in the maximum light output regions of the television tube and improved attenuation in other spectral regions.
A further object of the invention is to provide a light filter for television screens which substantially reduces glare and eye strain, and which comprises one or more glass sheets and a plastic interlayer treated with a suitable dyestutf to impart to said filter the foregoing noted improved characteristics.
A further object of the invention is to provide a laminated television screen having a plastic interlayer securing a pair of glass sheets in unitary relation, which interlayer preferably has an index of refraction substantially the same as that of the glass and which is dyed with a substance which imparts fast and clear color to the interlayer.
A still further object of the invention lies in the provision of a method of producing laminated television screens comprising dyeing a plastic interlayer with a suitable dyestuff, assembling the interlayer between sheets of glass, and applying heat and pressure to the assembly to bond the same into a composite structure.
Other objects and advantages of the invention will become more apparent during the course of the following description when taken in connection with the accompanying drawings.
In the drawings wherein like numerals are employed to designate like parts throughout the same:
FIG. 1 is a perspective view of a laminated television screen of this invention;
FIG. 2 is a diagrammatic perspective view of apparatus suitable for dyeing plastic sheeting employed as the interlayer in the present screen;
FIG. 3 is a curve showing the light output of the phosphor which is used in many commercial television picture tubes;
FIGS. 4, 5 and 6 are spectral transmittance curves of typical television screens embodying the features of the invention herein disclosed; and
FIG. 7 is a diagrammatic view showing the television screen positioned in front of a cathode ray tube.
In accordance with the present invention, a light filter or viewing screen for television receivers is provided comprising one or more sheets of a transparent material such as glass, either clear or tinted, and a plastic layer bonded thereto, said layer being preferably formed of a thermoplastic resinous material such as polyvinyl butyral which has been treated with a solution which may com- Patented Nov. 14, 1961 prise an alcohol, water, and a molecularly dispersed organic dyestuff such as Capracyl Black N with or without additives, which may be Capracyl Blue G or Anthraquinone Blue SWF. Dependent upon the composition and concentration of the dye solution, as well as on the duration of the dyeing operation, light filters may be produced which have a total visible luminous transmittance (LCJ. Ill. A) ranging between 30 and and a haze factor of not more than one percent. Although it is believed that the noted dyestuffs are molecularly dispersed, it is of course possible, depending upon the concentration of solution, temperature, and type of solvents, that they be associated to a greater or lesser degree.
While experience has indicated thta one or more oftthe foregoing noted dyestuffs produces the desired light trans mittance characteristics, as well as a substantial increase in picture clarity, it will be appreciated that other (lye substances may at times be found particularly suitable.
Thus, while each of the noted substances is well adapted to the present process by virtue of its water soluble and water-alcohol soluble nature, oil (organic solvent) soluble type dyestuffs having the proper spectral characteristics are also of considerable practical importance.
The Capracyl Black N and Blue G dyestuffs which have been found particularly suitable to accomplish the purposes of the present invention are neutral dyeingrnetallized azo dyes. Capracyl Black N is listed in the Technical Manual of the American Association of Textile Chemists and Colorists, vol. XXXV, part 5, 1959 edition on page 244, right-hand column line 32; and the color index number of Capracyl Blue G is Acid Blue 165." Anthraquinone Blue SWF is identified as prototypeNuInber 12. (Color Index No. Acid Blue 25).
With reference now to the drawings, there is shown in FIGURE 1 thereof a laminated television screen or light filter, designated in its entirety by the numeral 10,'which comprises a pair of glass sheets 11 and 12 anda plastic interlayer 13 bonded under heat and pressure to the inner face of each of said glass sheets. The glass forming said sheets is preferably that often referred to as ordinary clear sheet glass, although in cetrain instances it may be found desirable to employ a tinted glass characterized by a somewhat different chemical composition. Ordinary sheet glass, preferably of double strength weight, and having no perceptible color is, however, effective to accomplish the purposes of this invention. Glass of'this type has a general composition approximating 72.80% SiO 0.15% Fe O 0.90% A1 0 0.50% TiO 8.50% CaO, 3.60% MgO, 13.10% Na o, 0.08% K 0, 0.30% 80,, and 0.07% As O A typical tinted glass, "which provides in a television screen relatively high attenuation in the red region of the spectrum, produces upon analysis a composition which varies around 72.50% SiO 0.50% Fe O 0.80% A1 0 0.30% Ti02, 8.90% CaO, 3.40% 'MgO, 13.20% Na O, 0.10% K 0, and 0.30% S0 Regardless of the particular composition of the sheet glass, however, it is desirable for strength purposes that the glass thickness be around 0.25 inch. Also, it may at times be preferred for optical reasons to employ "plate glass rather than sheet glass. 1 t
The plastic interlayer 13 of the light filter 10 is preferably forrned of polyvinyl butyral resin, and as examples of materials which have been found particularly suitable are those designated as Saflex, manufactured and 'sold by Monsanto Chemical Co., Butacite by E. I. du Pont de Nemours and Co., and fVinal by Carbide and Chemicals Corp. As employed between the glass sheets 11 and 12, or when laminated to the face of a' television receiver tube, the interlayer 13 preferably comprises parts by weight of polyvinyl butyral resin and either 41 parts by weight of tri-ethylene glycol di-hexoate 0:40
parts by weight of dibutoxyethyl adipate. With the latter compound in the amount indicated the resin contains 29% of plasticizer, and with the former, 28.6% of plasticizer. Resinous materials other than polyvinyl butyral may of course be used, such as for example, polyvinyl formal and acetal.
Dyeing of the plastic interlayer to a neutral gray color sufficient to produce when laminated with two sheets of glass a total visible light transmittance ranging between 30 and 80% and a haze value normally less than one percent is accomplished on apparatus of the character shown in FIGURE 2. The continuous dyeing machine illustrated therein preferably comprises a primary wash section A, a dyeing section B, and a rinse or secondary wash section C. Positioned adjacent the section A is a pair of drive rolls 14 which draws plastic sheeting 15 from a supply roll 16 into the wash section A between hot water sprays 17 and beneath an idler roll 18. The sheeting 15 is then drawn upwardly between cold water sprays 19 by means of a pair of drive rolls 20, and a large portion of the excess water on said sheeting is removed by a pair of wringer rolls 21 adjacent which are compressed air jets 22 for substantially drying the now thoroughly washed sheeting 15. Idler rolls 23 are provided adjacent the base of the dyeing section B and the sheeting passes beneath said rolls and through the dye solution 24 prior to its movement upwardly and between an additional pair of wringer or squeegee rolls 25 which are partially immersed in said solution.
Thereafter the sheeting 15 continues into the rinse or secondary wash section C wherein there are located cold water sprays 26 directed at opposite surfaces of the dyed sheeting and an idler roll 27 under which the plastic matei'ial passes prior to being drawn upwardly between spaced pairs of wringer rolls 28 and 29 by the drive rolls 30. Two spaced pairs of compressed air jets 31 and 32 are located forwardly of said drive rolls, and positioned between said pairs of jets are electric radiant heaters 33 which operate to reduce the dye solution solvent which has been absorbed into the sheeting. A trough of dusting material 34, such as sodium bicarbonate, is provided in the path of the moving plastic material, and after being dusted, said material is rolled up into a form suitable for cutting into sizes for use as an interlayer in the present invention. Thereafter the plastic is oven-dried to remove last traces of solvent, is then festooned and cut, and is next rapidly washed to remove the sodium bicarbonate dusting powder.
In the operation of the foregoing described apparatus the dyeing procedure is preferably initiated by first turning on the water sprays 17 in the wash section A and feeding the plastic sheeting into the dyeing machine. Dye solution 24 is then pumped into the dye section B to a level sufficienjt to partially immerse the pair of squeegee rolls 25 located at the exit end of the dye bath or section B. A supply of water to the rinse section C and compressed air to the jets 22, 31 and 32 is then furnished, and the radiant heaters 33 and motor means (not shown) operating the drive rolls 14, 20, 29 and 30 turned on. Tension is maintained on the platsic, and wrinkling thereof avoided as it passes through the wash sections A and C, by operating the drive rolls 14 at a speed generally about slower than the squeegee or wringer rolls 21,
and by maintaining substantially the same relation between the rolls 20, 23 and 25 and the wringer ro'lls 28 and 29. It has also been found important that the dye solution. 24 be maintained at a constant level in contact with the wringer rolls 25 throughout the operation, and that uniform and complete coverage of the plastic sheeting 15 by the cold water sprays 26 in the rinse section C be accomplished in order to remove excess dye solution and absorbed alcohol from said sheeting.
Plastic sheeting dyed in accordance with the disclosed procedure has, when laminated by conventional techniques under heat and pressure between sheets of either clear or tinted glass, a total visible light transmittance (hereinafter referred to as TVLT) with illuminant A of between 30 and and a haze factor or light scattering characteristic of substantially less than one percent, the TVLT being dependent upon the composition and concentration of the dye solution, and the speed of passage of the sheeting through the dyeing procedure. The total visible luminous transmittance of the television screen herein disclosed is preferably determined by optical bench measurements on the unlaminated dyed plastic since experience has indicated that the transmittance value for the dyed plastic alone seldom varies more than one percent from the TVLT of the laminated screen itself when employing ordinary sheet glass. Rather than determining the total transmittance by optical bench methods, it will of course be appreciated that Illuminant A total transmittance may be calculated from the spectral transmission curve of the dyed plastic determined by a spectrophotometer before or after lamination with glass sheets. The haze value, on the other hand, depends largely on the nature and composition of the plastic itself, and is readily determined in accordance with A.S.T.M. Designation: D100349T.
Since, on the average, undyed polyvinyl butynal plastic when laminated between two clear glass sheets of the exemplary composition earlier noted produces a structure having a total transmittance (TVLT-Ill. A) of around 89.5%, and when laminated between tinted glass sheets of the exemplary composition also noted, results in a laminate having a TVLTIll. A of approximately 74.0%, it will be readily seen by the following illustrative examples as to the extent to which the total transmittance is reduced and substantial improvement in light contrast and picture definition accomplished.
Example 1 A sheet of polyvinyl butyral having a plasticizer content of approximately 29% was dip dyed for 6% minutes at 75 F. in a dye bath containing 2.5 grams of Capracyl Black N dyestuff dissolved in one liter of a solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of distilled water. A neutral color was produced in the plastic, and optical measurements indicated the plastic had a total visible light transmittance (TVLT) of 43% and a haze factor of 0.9%. The plastic was then laminated between single sheets of double strength sheet glass.
Example 2 A sheet of the same type of plastic was dip dyed for 6 /2 minutes at 75 F. in a blended dye bath of two parts by volume of Capracyl Black N as in Example 1 plus one part by volume of blue composed of 2.5 grams of Capracyl Blue G, dissolved in one liter of the same solvent used in the above example. The plastic had a neutral blue color, and a TVLT of 42% and a haze factor of 0.6%. It was then laminated as above.
Example 3 A sheet of the same type of plastic was dip dyed for 6 minutes at 75 F. in a blended dye bath containing 2 parts of black to 3 parts of blue by volume. The black bath contained 2.5 grams of Capracyl Black N dyestuff dissolved in one liter of a solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of water. The blue bath was prepared in the same concentration and solvent system with Capracyl Blue G dyestutf. Upon measurement the plastic had a TVLT of 45% and a haze factor of 0.5%. A laminate was then produced as previously.
Example 4 position earlier noted. A product resulted having a TVLT of 38% and a haze factor of 0.6%.
Example 5 A plastic sheet dyed in the same manner as in the second example was laminated between two sheets of a tinted glass as above. The laminate thus formed had a TVLT of 37% and a haze factor of 0.5%.
Example 6 A plastic sheet dyed in the same manner as in the third example was laminated between two sheets of a tinted glass as above. It was found that the laminate had a TVLT of 37% and a haze factor of 0.8%.
Example 7 A sheet of polyvinyl butyral resin manufactured and sold by Monsanto Chemical Co., under the name Neutralite, and which has carbon black pigment dispersed within the plastic itself, was laminated between sheets of a tinted glass. It was noted that the laminate had a TVLT of 48.5% and a haze factor of 2.37%.
Example 8 The same type plastic as in the last example was laminated between two pieces of clear sheet glass. Optical measurements on the laminate produced a TVLT of 57.6% and a haze factor of 1.5%.
Example 9 A sheet of monolithic methyl methacrylate plastic proposed for television screens and having a thickness of 0.0575 inch, as compared to 0.015 inch in the last two examples, was ex'amined and found to have a'TVLT of 44.0% and a haze factor .of 3.7%.
Example 10 A sheet of the same type polyvinyl butyral resin as in the first six examples was dip dyed for one minute at 75 F. in a dye bath containing 2.5 grams Capracyl Black N dyestuff dissolved in one liter of solvent .composed of 60 pants by volume of ethyl alcohol and 40.parts 'by volume of distilled water. The dyed plastic was rinsed with water and noted to be of a neutral shade. It was found to have a TVLT of 55% and a hazefactor of 0.3%. The sheeting was then laminated with sheets of tinted glass.
Example 11 A sheet of the same type of plastic was dyed and rinsed in the same manner as in Example 10. The dye bath was of the following composition: Five parts by volume of a black bath containing 2.5 grams Capracyl Black N dissolved in one liter of a solvent composed of 60 parts by volume of denatured ethyl alcohol and 40 parts by volume of water plus one part by volume of a blue bath prepared with Anthraquinone Blue SWF dyestuff in the same concentration and solvent system. The TVLT of the resinous layer was 57% and the haze .factor 0.35%. A laminate was formed as above.
Example 12 The same type plastic as above was dyed with the same solution as Example 10, the dyeing time being increased to two minutes in the bath. It was noted that doubling the dip time decreased the TVLT to 50% and the haze factor was 0.25%. A laminate of the same structure as above was made.
Example 13 The same procedure as in the last example was followed in the dyeing of polyvinyl butyral resin with the dye solution of Example ll. The increase in dipping time reduced the TVLT to 51% and the dyed plastic had a haze factor of 0.3%. A tinted glass was used in making a laminate.
Example 14 Polyvinyl butyral sheeting was dipped for one minute at 75 F. in a Capracyl Black N dye bath of the following composition: Two and one-half grams of dyestuif dissolved in one liter of solvent composed of 60 parts by volume of ethyl alcohol and 40 parts by volume of water. The dyed sheeting was found to have a TVLT of 64.5% and a haze factor of less than 1%.
Example 15 A dye solution was prepared containing a mixture of sixty gallons of denatured ethyl alcohol and forty gallons of distilled water, to which was added with stirring plastic per minute therethrough, and the solution is prepared as above, the total visible light transmittance (III. A) of the dyed sheeting will continuously remain at 42.5% plus or minus 3.0%, and that the haze factor will be in the neighborhood of 0.25 and 0.35%.
It may thus be seen from the foregoing illustrative examples that a plastic .interlayer for use in television screens may be produced having substantially any particular light transmittance for any specific television tube by accurate control of the composition and concentration of the dye solution, by careful regulation of the rate of feed or time absorbed in passing the plastic through the dye bath, and by selection of the desired type of glass used inthe'laminate. Further, when combined with sheets or plates of glass, the plastic may be laminated to any desired thickness with an increase in the safety factor by merely using a plastic inter-layer of greater thickness, as for example, to 0.045 inch, or by increasing the number of layers of 0.015 inch plastic. By this means a substantial advantage accrues over presently used implosion plates of tempered plate glass.
It will also be appreciated that while waterand wateraloohol soluble dyestuffs are preferred, oil soluble type dyestuffs of the proper spectral characteristics may also be employed. And since, in using the latter dyestuffs in the dip-dyeing process disclosed we have found that the dye solvent attacked the plastic interlayerand removed substantial quantities of plasti-cizcr from the interlayer, we prefer the use of a silk screening or printing process. Here the oil soluble type dyestuff is dissolved in a plasticizer or solvent plasticizer mixture and then applied to the surface of the sheeting using silk screens or printing rolls. However, when the dyestuff is applied by either of these two methods, it is left in discreet particles on the surface of the sheet plastic, and it has therefore been found necessary to heat the plastic subsequent to the application of the dycstuif in order to accomplish diffusion of the dyestuff uniformly throughout the body of the inter- .layer sheet material.
To illustrate the variations which'may be accomplished in light transmittances, there is shown in FIGURE 3, a curve of the light output of the P4 phosphor which is used in many of the commercial television picture tubes. From this it may be seen that the particular phosphor plotted peaks or has its maximum light output at slightly less than 440 millimicrons or 4400 Angstrom units when the relative intensity or energy is between 82 and 83, and at about 550 millimicrons or 550 Angstrom units when the relative intensity is about 78. Comparing this with the curve of FIGURE 4, which shows the spectral trans mi-ttanoe for the light filter produced in accordance with the procedure of Example 2 above, it will be seen that said 7 screen has a transmittance of about 39% at 440 millimicrons and about 41.5% at 550 millimicrons, the peaks of the P4 phosphor. It therefore attenuates well in the maximum output regions, and has a TVLT of 42% which is effective for the desired improvement in image contrast and clarity, as well as picture definition.
FIGURE 5 plots the spectral transmittance of a television screen which has been manufactured according to Example 4. It will be noted that this screen has a 37.5% transmittance at about 440 millimicrons and substantially the same transmittance at about 550 millimicrons, the peaks of the same phosphor tube as shown in FIG. 3. As was brought out in this particular example, the screen had a total visible transmittance of 38% and a haze factor of 0.6%. Since the dyed plastic was laminated between two sheets of tinted glass, such as screen possesses a high attenuation in the red regions of the spectrum.
FIGURE 6 illustrates a curve of wavelength plotted against percent transmittance for a screen produced in accordance with Example 14 and which has a TVLT of 64.5%. It may be seen that such a screen has a transmittance of 614% at 440 millimicrons and 63.7% at 550 millimicrons. It has been found to have particular utility in connection with television picture tubes which have a light output slightly lower than that of the tube plotted in FIGURE 3.
The P4 phosphor screen, designated as such by the Radio Manufactin ers Association to indicate its use in monochrome (black and white) television, is considered to be a twocomponent screen comprising a blue-emitting and a yellow emitting phosphor. For this purpose, most unalurninized P4 screens for direct viewing kinescopes presently comprise admixed hex.-ZnS:Ag (blue component) and hex.-ZnS(47) CdS(53):Ag (yellow component). These two sulphide phosphors have closely matched emission characteristics as a function of cathode ray current density, and screens made of the two phosphors give uniform white emission in image half-tones andhigh lights.
To our knowledge there are three cathode ray tube screens which have been coded by the Radio Manufacturers Association as P4 phosphor screens and with which the present invention is of particularly important application. The first, which may be referred to as P4(a) is understood to be formed of a mixture of hex.-ZnS: Ag(0.0l5) and hex.-l.3 ZnS-CdS:Ag(0.0l). The second, P4(b), presumably consists of hex.-ZnS:Ag(0.)l5) or a mixture of cub.-ZnS:Ag(0.003-0.0l) and rbhdl.- Zn BeSi O :Mn(l.4). The third, P4(c), is understood to comprise as the representative phosphor monocL-Ca Mg(SiO :Ti(l) plus rbhdl.-Zn BeSi O :Mn(1.4).
Each of the foregoing P4 phosphors not only differ in composition but has slightly different peaks or regions of maximum light output. Thus, the P4(a) phosphor with which we are most familiar and the light output curve of which is plotted in FIG. 3 of the accompanying drawings, peaks at about 4400 and 5500 Angstrom units, while the P4(b) and P4(c) phosphors peak at about 4600 and 5400 Angstroms and 4000 and 5400 Angstrom units, respectively.
Since each of the noted P4 phosphors have particular utility in television kinescopes of the monochrome type and emit white light both before and after excitation, with the exception of the P4( b) type which emits greenyellow light after excitation only, the present invention is of application to cathode ray tubes utilizing either of these representative phosphors. Thus, laminated television screens of the character herein disclosed will be found to attenuate well and to provide improved picture clarity with cathode ray tubes which have regions of maximum light output between 400 and 480 millimicrons and between 500 and 580 millimicrons.
A cathode ray tube of the above character for' television receivers is illustrated in FIGURE 7, and upon reference thereto, it will be noted that said tube 35 is provided with a picture face 36 carrying on its inner surface a phosphor coating 37. To accomplish the purposes of the present invention, the viewing screen or light filter 10 herein disclosed is positioned in front of and closely adjacent to the picture face 36. If desired, the plastic interlayer 13 provided between the glass sheets 11 and 12 of said screen 10 may be formed of a plurality of plastic sheets, one or more of which may be dyed as above described and one or more of which may be of substantially clear undyed plastic.
It is to be understood that various modifications may be made in the compositions and procedures herein disclosed without departing from the spirit and scope of the invention as defined in the appended claims.
We claim:
1. In a television receiver, a cathode ray tube provided with a picture face carrying a phosphor coating, and a viewing screen spaced in front of and closely adjacent to said picture face, said phcsphor coating being a member of the group consisting of a mixture of rbhdl.-Zn BeSi O :Mn(1.4)
monocl.-CaMg(SiO 3 :Ti( 1 and plus
rbhdl-zn lieSi o zMnflA) said viewing screen carrying an organic dye stuff of the neutral dyeing metallized azo dye type.
2. In a television receiver of the character defined in claim 1, in which said viewing screen comprises a sheet of glass and a sheet of dyed plastic material bonded to said glass sheet, said plastic material carrying the azo dye.
3. In a television receiver of the character defined in claim 2, in which the dyed sheet of plastic material has regions of minimum visible light transmittance between 400 and 460 millimicrons and between 520 and 560 millimicrons.
4. In a television receiver, a cathode ray tube provided with a picture face carrying a phosphor coating having two regions of maximum light output, one between 400 and 480 millimicrons and one between 500 and 580 millimicrons, and a viewing screen spaced in front of and closely adjacent to said picture face, said viewing screen comprising a sheet of glass and a sheet of plastic material colored a neutral gray with a metallized azo dyestudf, said colored plastic sheet having a total visible luminous transmittance (I.C.I. Ill. A) effective to attenuate the White light emitted by said tube within both the maximum light output regions of said phosphor to provide better image contrast and clarity as well as picture definition.
5. In a television receiver of the character defined in claim 4, in which the plastic sheet has been colored in neutral gray with a solution which includes Capracyl Black N dyestuff.
6. In a television receiver of the character defined in claim 4, in which the plastic sheet has been colored a neutral gray with a solution which includes Capracyl Black N dyestuff and a dyestufi selected from the group consisting of Capracyl Blue G dyestuff and Anthraquinone Blue SWF dyestufi.
7. A sheet of transparent plastic material for use as a viewing screen in a television receiver carrying an organic dyestufI' of the neutral dyeing metallized azo dye type.
8. A sheet of polyvinyl butyral carrying an organic dyestufi of the neutral dye metallized azo dye type for use as a viewing screen in a television receiver.
9. In a television receiver having a cathode ray tube provided with a picture face carrying a phosphor coating,
said phosphor coating being a member of the group consisting of a mixture of hex.-ZnS:Ag(0.0l) and hex-1.3 ZnS-CdS:Ag(0.0l); hex.-ZnS:Ag(0.015) or a mixture of cub. ZnS:Ag(0.003-0.0l) and rbhdl. ln Besi O zMn (1.4); and monocl. CaMg(SiO :Ti(1) plus rbhdl. Zn BeSi O :Mn( 1.4), the improvement of a viewing Screen spaced in front of and closely adjacent to said picture face, said viewing screen comprising a sheet of glass and a sheet of plastic material bonded to said sheet of glass, said plastic material being colored a neutral grey with a metallized azo dyestuif, said colored plastic sheet having a total visible luminous transmittance (I.C.I. Ill. A) effective to attenuate the white light emitted by said tube within both the maximum light output regions of said phosphor to provide better image contrast and clarity aswell as picture definition.
10. In a television receiver of the character defined in claim 9, in which the dyed sheet of plastic material has regions of minimum visible light transmittance between 400 and 460 millimicrons and between 520 and 560 millimicrons.
11. In a teievision receiver of the characted defined in claim 9 in which. the plastic sheet has been colored a neutral grey with a solution which includes Capracyl Black N dyestufi.
12. In a television receiver of the character defined in claim 9 in which the plastic sheet has been colored a neutral grey with a solution which includes Capracyl Black N dyestuff and a dyestuif selected from the group consisting of Capracyl Blue G dyestutf and Anthraquinone Blue SWF dyestufi'v Reierences Cited in the file of this patent UNITED STATES PATENTS 2,188,160 Rooney et a1 Jan. 23, 1940 2,260,543 Smith Oct. 28, .1941 2,308,732 White Jan. 19, 1943 2,445,774 Gorn July 27, 1948 2,461,464 Aronstein Feb. 8, 1949 2,476,619 Nicoll July 19, 1949 2,481,622 Rosenthal Sept. 13, 1949 2,567,714 Kaplan Sept. 11, 1951 2,606,241 Steinke Aug. 5, 1952 2,609,269 Ryan et a1 Sept. 2, 1952 2,655,452 Barnes et a1. Oct. 13, 1953 2,690,554 Wolf Sept. 28, 1954 FOREIGN PATENTS 706,190 Great Britain Mar. 24, 1954 OTHER REFERENCES Publication 1: Journal of the Society of Dying and Colouring, pages 306-310, an article The Colouring of Plastics, by Oehlcke. Dec. 1945. (Copy Div.
Publication '11: The Technical Bulletin, Dec. 1951, a publication titled the Coloration of Plastics, pages 203- 222. Published by the Dupont Co. (Copy in Div. 45).

Claims (1)

  1. 4. IN A TELEVISION RECEIVER, A CATHODE RAY TUBE PROVIDED WITH A PICTURE FACE CARRYING A PHOSPHOR COATING HAVING TWO REGIONS OF MAXIMUM LIGHT OUTPUT, ONE BETWEEN 400 AND 480 MILLIMICRONS AND ONE BETWEEN 500 AND 580 MILLIMICRONS, AND A VIEWING SCREEN SPACED IN FRONT OF AND CLOSELY ADJACENT TO SAID PICTURE FACE, SAID VIEWING SCREEN COMPRISING A SHEET OF GLASS AND A SHEET OF PLASTIC MATERIAL COLORED A NEUTRAL GRAYWITH A METALLIZED AZO DYESTUFF, SAID COLORED PLASTIC SHEET HAVING A TOTAL VISIBLE LUMINOUS
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US3059051A (en) * 1957-02-16 1962-10-16 Detag Optical filters
US3078343A (en) * 1955-10-19 1963-02-19 Siemens Ag Television receiver comprising an optical filter
US3200188A (en) * 1962-03-21 1965-08-10 Telefunken Patent Cathode ray tubes with insulated implosion protective frame
US3992141A (en) * 1972-11-21 1976-11-16 Foster Grant Co., Inc. Method of and apparatus for treating plastic film
US4675252A (en) * 1984-04-18 1987-06-23 Nippon Kayaku Kabushiki Kaisha Base material having a dyed membrane on the surface thereof, and method for dyeing a membrane thereon
US4709272A (en) * 1985-06-14 1987-11-24 Standard Elektrik Lorenz Implosion protection for video reproducing device

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US2188160A (en) * 1936-10-09 1940-01-23 Colancse Corp Of America Coloration of artificial textile and other materials
US2260543A (en) * 1937-05-22 1941-10-28 Carbide & Carbon Chem Corp Method for coloring plastic resins
US2308732A (en) * 1940-04-20 1943-01-19 Du Pont Colored cellulosic film
US2445774A (en) * 1945-08-20 1948-07-27 Raytheon Mfg Co Picture receiver utilizing anomalous reflection from silver
US2461464A (en) * 1947-11-14 1949-02-08 Aronstein Robert Filter for fluorescent screens
US2476619A (en) * 1946-08-23 1949-07-19 Rca Corp Cascade phosphor screen
US2481622A (en) * 1945-06-06 1949-09-13 Skiatron Corp Cathode-ray tube with photo-dichroic ionic crystal light modulating screen
US2567714A (en) * 1950-12-21 1951-09-11 Sightmaster Corp Cathode-ray tube
US2606241A (en) * 1949-12-17 1952-08-05 Zenith Radio Corp Cathode-ray tube supporting structure
US2609269A (en) * 1948-11-18 1952-09-02 Libbey Owens Ford Glass Co Glare screen
US2655452A (en) * 1950-05-13 1953-10-13 American Optical Corp Glasses, compositions, thereof, articles embodying said glasses, and method of making and using the same
GB706190A (en) * 1950-12-14 1954-03-24 Gen Electric Co Ltd Improvements in or relating to apparatus for viewing television and other images on the screens of cathode ray tubes
US2690554A (en) * 1950-03-09 1954-09-28 American Optical Corp Ultraviolet filter for cathode-ray tubes

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US2188160A (en) * 1936-10-09 1940-01-23 Colancse Corp Of America Coloration of artificial textile and other materials
US2260543A (en) * 1937-05-22 1941-10-28 Carbide & Carbon Chem Corp Method for coloring plastic resins
US2308732A (en) * 1940-04-20 1943-01-19 Du Pont Colored cellulosic film
US2481622A (en) * 1945-06-06 1949-09-13 Skiatron Corp Cathode-ray tube with photo-dichroic ionic crystal light modulating screen
US2445774A (en) * 1945-08-20 1948-07-27 Raytheon Mfg Co Picture receiver utilizing anomalous reflection from silver
US2476619A (en) * 1946-08-23 1949-07-19 Rca Corp Cascade phosphor screen
US2461464A (en) * 1947-11-14 1949-02-08 Aronstein Robert Filter for fluorescent screens
US2609269A (en) * 1948-11-18 1952-09-02 Libbey Owens Ford Glass Co Glare screen
US2606241A (en) * 1949-12-17 1952-08-05 Zenith Radio Corp Cathode-ray tube supporting structure
US2690554A (en) * 1950-03-09 1954-09-28 American Optical Corp Ultraviolet filter for cathode-ray tubes
US2655452A (en) * 1950-05-13 1953-10-13 American Optical Corp Glasses, compositions, thereof, articles embodying said glasses, and method of making and using the same
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3078343A (en) * 1955-10-19 1963-02-19 Siemens Ag Television receiver comprising an optical filter
US3059051A (en) * 1957-02-16 1962-10-16 Detag Optical filters
US3200188A (en) * 1962-03-21 1965-08-10 Telefunken Patent Cathode ray tubes with insulated implosion protective frame
US3992141A (en) * 1972-11-21 1976-11-16 Foster Grant Co., Inc. Method of and apparatus for treating plastic film
US4675252A (en) * 1984-04-18 1987-06-23 Nippon Kayaku Kabushiki Kaisha Base material having a dyed membrane on the surface thereof, and method for dyeing a membrane thereon
US4709272A (en) * 1985-06-14 1987-11-24 Standard Elektrik Lorenz Implosion protection for video reproducing device

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